Semiconductor device and method of manufacturing the same

ABSTRACT

Oxygen is released from the insulating layer, whereby oxygen deficiency in the oxide semiconductor layer and an interface state between the insulating layer and the oxide semiconductor layer can be reduced. Accordingly, a semiconductor device where reliability is high and variation in electric characteristics is small can be manufactured.

This application claims priority from Japanese Patent Application SerialNo. 2010-117753 filed on May 21, 2010 in Japan.

TECHNICAL FIELD

The present invention relates to a semiconductor device and a method formanufacturing the semiconductor device.

In this specification, a semiconductor device means a general devicewhich can function by utilizing semiconductor characteristics, and anelectro-optic device, a semiconductor circuit, and an electronic deviceare all semiconductor devices.

BACKGROUND ART

A technique by which transistors are formed using semiconductor thinfilms formed over a substrate having an insulating surface has beenattracting attention. Such transistors are applied to a wide range ofelectronic devices such as an integrated circuit (IC) or an imagedisplay device (display device). As materials of semiconductor thinfilms applicable to the transistors, silicon-based semiconductormaterials have been widely used, but oxide semiconductors have beenattracting attention as alternative materials.

For example, disclosed is a transistor whose active layer is formedusing an amorphous oxide containing indium (In), gallium (Ga), and zinc(Zn) and having an electron carrier concentration of less than 10¹⁸/cm³(see Patent Document 1).

A transistor including an oxide semiconductor is known to have a problemof low reliability because of high possibility of fluctuation inelectric characteristics, although the transistor including an oxidesemiconductor can operate at higher speed than a transistor includingamorphous silicon and can be manufactured more easily than a transistorincluding polycrystalline silicon. For example, the threshold voltage ofthe transistor fluctuates between before and after a bias-temperaturetest (BT test). Note that in this specification, a threshold voltagerefers to a gate voltage which is needed to turn on the transistor.“Gate voltage” refers to a potential difference between a source and agate when the potential of the source is used as a reference potential.

[Reference]

[Patent Document]

[Patent Document 1] Japanese Published Patent Application No.2006-165528

DISCLOSURE OF INVENTION

Fluctuation in the threshold voltage due to a BT test of the transistorincluding an oxide semiconductor reduces the reliability of thetransistor including an oxide semiconductor. An object of one embodimentof the present invention is to improve reliability of a semiconductordevice including an oxide semiconductor.

One embodiment of the present invention is a semiconductor device or amethod for manufacturing the semiconductor device which is based on thetechnical idea to form an insulating layer containing a silicon peroxideradical as an insulating layer in contact with an oxide semiconductorlayer in a transistor including an oxide semiconductor.

In silicon oxide, silicon is stable in a form of (O—)₃Si—O; however, aradical like (O—)₃Si. is formed when one of the oxygen atoms iseliminated by heat or the like. When O₂ is bonded here, (O—)₃Si—O—O. (asilicon peroxide radical) is formed. The silicon peroxide radicalbecomes a stable state when oxygen is supplied outside of the siliconperoxide radical.

“Containing a silicon peroxide radical” in a material including siliconoxide means that signals can be seen at g value=2.0078 and 2.0016 in aspectrum obtained by an electron spin resonance (ESR) method.

One embodiment of the present invention is a semiconductor device or amethod for manufacturing the semiconductor device which is based on thetechnical idea to form an insulating layer containing a silicon peroxideradical as a base insulating layer and a gate insulating layer in atop-gate transistor including an oxide semiconductor.

When a silicon peroxide radical is contained in the base insulatinglayer, it is possible to sufficiently suppress trapping of a charge orthe like, which can be generated due to the operation of a semiconductordevice, or the like, at an interface between the base insulating layerand an oxide semiconductor layer. This advantageous effect is broughtabout because an interface state between the oxide semiconductor layerand the base insulating layer can be reduced by supplying oxygen fromthe base insulating layer to the oxide semiconductor layer.

In addition, when a silicon peroxide radical is contained in the gateinsulating layer, it is possible to sufficiently suppress trapping of acharge or the like, which can be generated due to the operation of asemiconductor device, or the like, at an interface between the gateinsulating layer and the oxide semiconductor layer. This advantageouseffect is brought about because an interface state between the oxidesemiconductor layer and the gate insulating layer can be reduced bysupplying oxygen from the gate insulating layer to the oxidesemiconductor layer.

Further, a charge is caused due to oxygen deficiency in the oxidesemiconductor layer in some cases. In general, the oxygen deficiency inthe oxide semiconductor layer becomes donors and generates electronswhich are carriers. As a result, the threshold voltage of the transistoris shifted in a negative direction. Oxygen is supplied to the oxygendeficiency in the oxide semiconductor layer from the base insulatinglayer and the gate insulating layer, whereby the shift of the thresholdvoltage in a negative direction can be suppressed.

In other words, when oxygen deficiency is caused in an oxidesemiconductor layer, it is difficult to suppress trapping of a charge atan interface between a base insulating layer and an oxide semiconductorlayer and an interface between a gate insulating layer and the oxidesemiconductor layer. However, by providing the base insulating layercontaining a silicon peroxide radical and the gate insulating layercontaining a silicon peroxide radical, the interface state and theoxygen deficiency in the oxide semiconductor layer can be reduced andthe adverse effect of the trapping of a charge at the interface betweenthe base insulating layer and the oxide semiconductor layer can be madesmall.

Thus, the advantageous effect according to one embodiment of the presentinvention is attributed to the base insulating layer containing asilicon peroxide radical and the gate insulating layer containing asilicon peroxide radical.

In one embodiment of the present invention, one of the base insulatinglayer containing a silicon peroxide radical and the gate insulatinglayer containing a silicon peroxide radical may be included. Both thebase insulating layer containing a silicon peroxide radical and the gateinsulating layer containing a silicon peroxide radical are preferablyincluded.

Since the trapping of a charge at the interface between the baseinsulating layer and the oxide semiconductor layer and the interfacebetween the gate insulating layer and the oxide semiconductor layer canbe suppressed, which is described above as the advantageous effect,malfunctions such as increase of an off-state current of the transistorincluding an oxide semiconductor and fluctuation in the thresholdvoltage can be suppressed, and further the reliability of thesemiconductor device can be improved.

Note that the base insulating layer containing a silicon peroxideradical preferably has an enough thickness with respect to the thicknessof the oxide semiconductor layer. This is because oxygen isinsufficiently supplied to the oxide semiconductor layer in some caseswhen the thickness of the base insulating layer containing a siliconperoxide radical is small with respect to the thickness of the oxidesemiconductor layer.

One embodiment of the present invention is a semiconductor deviceincluding a base insulating layer, an oxide semiconductor layer, asource electrode and a drain electrode electrically connected to theoxide semiconductor layer, a gate insulating layer partly in contactwith the oxide semiconductor layer, and a gate electrode over the gateinsulating layer, and at least one of the base insulating layer and thegate insulating layer contains a silicon peroxide radical.

In the above structure, the base insulating layer can be formed usingsilicon oxide, silicon oxynitride, silicon nitride oxide, aluminumoxide, or a stacked layer including any of these. The gate insulatinglayer can be formed using silicon oxide, silicon oxynitride, aluminumoxide, hafnium oxide, or a stacked layer including any of these. Notethat the base insulating layer and the gate insulating layer on the sidein contact with the oxide semiconductor layer are formed using siliconoxide or silicon oxynitride.

In this specification, silicon oxynitride refers to a substance thatcontains more oxygen than nitrogen and for example, silicon oxynitrideincludes oxygen, nitrogen, silicon, and hydrogen at concentrationsranging from greater than or equal to 50 atomic % and less than or equalto 70 atomic %, greater than or equal to 0.5 atomic % and less than orequal to 15 atomic %, greater than or equal to 25 atomic % and less thanor equal to 35 atomic %, and greater than or equal to 0 atomic % andless than or equal to 10 atomic %, respectively. Further, siliconnitride oxide refers to a substance that contains more nitrogen thanoxygen and for example, silicon nitride oxide includes oxygen, nitrogen,silicon, and hydrogen at concentrations ranging from greater than orequal to 5 atomic % and less than or equal to 30 atomic %, greater thanor equal to 20 atomic % and less than or equal to 55 atomic %, greaterthan or equal to 25 atomic % and less than or equal to 35 atomic %, andgreater than or equal to 10 atomic % and less than or equal to 25 atomic%, respectively. Note that rates of oxygen, nitrogen, silicon, andhydrogen fall within the above ranges in the cases where measurement isperformed using Rutherford backscattering spectrometry (RBS) or hydrogenforward scattering spectrometry (HFS). In addition, the total of thepercentages of the constituent elements does not exceed 100 atomic %.

In the above structure, a protective insulating layer which covers thegate insulating layer and the gate electrode may be provided in somecases. Further, a conductive layer may be provided below the oxidesemiconductor layer in some cases.

One embodiment of the present invention is a semiconductor device or amethod for manufacturing the semiconductor device which is based on thetechnical idea to form an insulating layer containing a silicon peroxideradical as a gate insulating layer and a protective insulating layer ina bottom-gate transistor including an oxide semiconductor.

When a silicon peroxide radical is contained in the protectiveinsulating layer, it is possible to sufficiently suppress trapping of acharge or the like, which can be generated due to the operation of asemiconductor device, or the like, at an interface between theprotective insulating layer and an oxide semiconductor layer. Thisadvantageous effect is brought about because an interface state betweenthe oxide semiconductor layer and the protective insulating layer can bereduced by supplying oxygen from the protective insulating layer to theoxide semiconductor layer.

In addition, when a silicon peroxide radical is contained in the gateinsulating layer, it is possible to sufficiently suppress trapping of acharge or the like, which can be generated due to the operation of asemiconductor device, or the like, at an interface between the gateinsulating layer and the oxide semiconductor layer. This advantageouseffect is brought about because an interface state between the oxidesemiconductor layer and the gate insulating layer can be reduced bysupplying oxygen from the gate insulating layer to the oxidesemiconductor layer.

Oxygen is supplied to the oxygen deficiency in the oxide semiconductorlayer from the protective insulating layer and the gate insulatinglayer, whereby the shift of the threshold voltage in a negativedirection can be suppressed.

In other words, when oxygen deficiency is caused in an oxidesemiconductor layer, it is difficult to suppress trapping of a charge atan interface between a protective insulating layer and an oxidesemiconductor layer and an interface between a gate insulating layer andthe oxide semiconductor layer. However, by providing the protectiveinsulating layer containing a silicon peroxide radical and the gateinsulating layer containing a silicon peroxide radical, the interfacestate and the oxygen deficiency in the oxide semiconductor layer can bereduced and the adverse effect of the trapping of a charge at theinterface between the protective insulating layer and the oxidesemiconductor layer can be made small.

Thus, the advantageous effect according to one embodiment of the presentinvention is attributed to the protective insulating layer containing asilicon peroxide radical and the gate insulating layer containing asilicon peroxide radical.

In one embodiment of the present invention, one of the protectiveinsulating layer containing a silicon peroxide radical and the gateinsulating layer containing a silicon peroxide radical may be included.Both the protective insulating layer containing a silicon peroxideradical and the gate insulating layer containing a silicon peroxideradical are preferably included.

Since the trapping of a charge at the interface between the protectiveinsulating layer and the oxide semiconductor layer and the interfacebetween the gate insulating layer and the oxide semiconductor layer canbe suppressed, which is described above as the advantageous effect,malfunctions such as increase of an off-state current of the transistorincluding an oxide semiconductor and fluctuation in the thresholdvoltage can be suppressed, and further the reliability of thesemiconductor device can be improved.

Note that the protective insulating layer containing a silicon peroxideradical preferably has an enough thickness with respect to the thicknessof the oxide semiconductor layer. This is because oxygen isinsufficiently supplied to the oxide semiconductor layer in some caseswhen the thickness of the protective insulating layer containing asilicon peroxide radical is small with respect to the thickness of theoxide semiconductor layer.

One embodiment of the present invention is a semiconductor deviceincluding a base insulating layer, a gate electrode, a gate insulatinglayer, an oxide semiconductor layer which is over the gate electrodewith the gate insulating layer interposed therebetween, a sourceelectrode and a drain electrode electrically connected to the oxidesemiconductor layer, and a protective insulating layer which is over thesource electrode and the drain electrode and partly in contact with theoxide semiconductor layer, and at least one of the protective insulatinglayer and the gate insulating layer contains a silicon peroxide radical.

In the above structure, the protective insulating layer can be formedusing silicon oxide, silicon oxynitride, silicon nitride oxide, aluminumoxide, or a stacked layer including any of these. The gate insulatinglayer can be formed using silicon oxide, silicon oxynitride, aluminumoxide, hafnium oxide, or a stacked layer including any of these. Notethat the protective insulating layer and the gate insulating layer onthe side in contact with the oxide semiconductor layer are formed usingsilicon oxide or silicon oxynitride.

Further, in the above structure, a conductive layer may be providedbelow the oxide semiconductor layer in some cases.

In each of the above structures, the channel length L of the transistor,which is determined by the distance between the source electrode and thedrain electrode, can be greater than or equal to 10 nm and less than orequal to 10 μm, preferably 0.1 μm to 0.5 μm. It is needless to say thatthe channel length L may be greater than or equal to 10 μm. The channelwidth W can be greater than or equal to 10 μm.

According to one embodiment of the present invention, a transistor whichhas a small off-state current, less variation in the threshold voltage,and stable electrical characteristics can be provided by providing aninsulating layer containing a silicon peroxide radical as an insulatinglayer in contact with an oxide semiconductor layer.

Alternatively, according to one embodiment of the present invention, asemiconductor device including a transistor, where electriccharacteristics are favorable and reliability is high, can be provided.

BRIEF DESCRIPTION OF DRAWINGS

FIGS. 1A to 1C are a top view and cross-sectional views showing anexample of a semiconductor device which is one embodiment of the presentinvention.

FIGS. 2A to 2D are cross-sectional views each showing an example of asemiconductor device which is one embodiment of the present invention.

FIGS. 3A to 3E are cross-sectional views showing an example of amanufacturing process of a semiconductor device which is one embodimentof the present invention.

FIGS. 4A to 4E are cross-sectional views showing an example of amanufacturing process of a semiconductor device which is one embodimentof the present invention.

FIGS. 5A to 5E are cross-sectional views showing an example of amanufacturing process of a semiconductor device which is one embodimentof the present invention.

FIGS. 6A to 6E are cross-sectional views showing an example of amanufacturing process of a semiconductor device which is one embodimentof the present invention.

FIGS. 7A to 7E are cross-sectional views showing an example of amanufacturing process of a semiconductor device which is one embodimentof the present invention.

FIGS. 8A to 8C each show one mode of a semiconductor device which is oneembodiment of the present invention.

FIG. 9 is a cross-sectional view showing one mode of a semiconductordevice which is one embodiment of the present invention.

FIG. 10 is a cross-sectional view showing one mode of a semiconductordevice which is one embodiment of the present invention.

FIG. 11 is a cross-sectional view showing one mode of a semiconductordevice which is one embodiment of the present invention.

FIGS. 12A to 12F each illustrate an electronic device as a semiconductordevice which is one embodiment of the present invention.

FIG. 13 shows a spectrum of a sample formed using one embodiment of thepresent invention, which is obtained by an electron spin resonancemethod.

FIG. 14 shows a spectrum of a sample formed using one embodiment of thepresent invention, which is obtained by an electron spin resonancemethod.

FIG. 15 shows a spectrum of a sample formed using one embodiment of thepresent invention, which is obtained by an electron spin resonancemethod.

FIG. 16 shows a spectrum of a sample formed using one embodiment of thepresent invention, which is obtained by an electron spin resonancemethod.

FIG. 17 shows a spectrum of a sample formed using one embodiment of thepresent invention, which is obtained by an electron spin resonancemethod.

FIG. 18 shows a spectrum of a sample formed using one embodiment of thepresent invention, which is obtained by an electron spin resonancemethod.

FIG. 19 is a cross-sectional view showing one mode of a semiconductordevice which is one embodiment of the present invention.

FIG. 20 shows a semiconductor device manufactured using one embodimentof the present invention.

FIGS. 21A and 21B each show a semiconductor device manufactured usingone embodiment of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described indetail with reference to the accompanying drawings. However, the presentinvention is not limited to the description below and it is easilyunderstood by those skilled in the art that the mode and details can bechanged variously. Therefore, the present invention is not construed asbeing limited to description of the embodiments described below. Indescribing structures of the present invention with reference to thedrawings, the same reference numerals are used in common for the sameportions in different drawings. Note that the same hatch pattern isapplied to similar parts, and the similar parts are not especiallydenoted by reference numerals in some cases.

Note that the ordinal numbers such as “first” and “second” in thisspecification are used for convenience and do not denote the order ofsteps or the stacking order of layers. In addition, the ordinal numbersin this specification do not denote particular names which specify thepresent invention.

[Embodiment 1]

In this embodiment, one embodiment of a semiconductor device and amethod for manufacturing the semiconductor device will be described withreference to FIGS. 1A to 1C, FIGS. 2A to 2D, FIGS. 3A to 3E, FIGS. 4A to4E, FIGS. 5A to 5E, FIGS. 6A to 6E, and FIGS. 7A to 7E.

FIGS. 1A to 1C are a top view and cross-sectional views of a transistor151 which is a top-gate top-contact type as an example of asemiconductor device according to one embodiment of the presentinvention. Here, FIG. 1A is a top view, FIG. 1B is a cross-sectionalview along A-B of FIG. 1A, and FIG. 1C is a cross-sectional view alongC-D of FIG. 1A. Note that in FIG. 1A, some of components of thetransistor 151 (for example, a gate insulating layer 112) are omittedfor brevity.

The transistor 151 in FIGS. 1A to 1C includes a base insulating layer102, an oxide semiconductor layer 106, a source electrode 108 a, a drainelectrode 108 b, the gate insulating layer 112, and a gate electrode 114over a substrate 100.

As a material of the base insulating layer 102, silicon oxide, siliconoxynitride, or the like may be used. Alternatively, the base insulatinglayer 102 may be formed using a stacked layer of the above material andsilicon oxide, silicon nitride, silicon oxynitride, silicon nitrideoxide, aluminum oxide, aluminum nitride, a mixed material of any ofthem, or the like. For example, when the base insulating layer 102 has astacked-layer structure of a silicon nitride layer, a silicon nitrideoxide layer, an aluminum oxide layer, or an aluminum nitride layer, anda silicon oxide layer, entry of moisture from the substrate 100 or thelike to the transistor 151 can be prevented. In the case where the baseinsulating layer 102 is formed to have a stacked-layer structure, alayer of silicon oxide or silicon oxynitride is preferably formed on aside where the base insulating layer 102 is in contact with the oxidesemiconductor layer 106. Note that the base insulating layer 102functions as a base layer of the transistor 151. Note that the baseinsulating layer 102 preferably contains a silicon peroxide radical.“Containing a silicon peroxide radical” in a material including siliconoxide means that signals can be seen at g value=2.0078 and 2.0016 in aspectrum obtained by an ESR method.

As a material used for the oxide semiconductor layer, anIn—Sn—Ga—Zn—O-based material which is a four-component metal oxide; anIn—Ga—Zn—O-based material, an In—Sn—Zn—O-based material, anIn—Al—Zn—O-based material, a Sn—Ga—Zn—O-based material, anAl—Ga—Zn—O-based material, or a Sn—Al—Zn—O-based material which arethree-component metal oxides; an In—Zn—O-based material, a Sn—Zn—O-basedmaterial, an Al—Zn—O-based material, a Zn—Mg—O-based material, aSn—Mg—O-based material, an In—Mg—O-based material, or an In—Ga—O-basedmaterial which are two-component metal oxides; an In—O-based material; aSn—O-based material; a Zn—O-based material; or the like can be used.Further, silicon oxide may be contained in the above material. Here, forexample, an In—Ga—Zn—O-based material means an oxide layer containingindium (In), gallium (Ga), and zinc (Zn), and there is no particularlimitation on the composition ratio. Further, the In—Ga—Zn—O-based oxidesemiconductor may contain an element other than In, Ga, and Zn. As anexample, in the case where an In—Zn—O-based material is used, any of thefollowing is employed: In/Zn is greater than or equal to 0.5 and lessthan or equal to 50 in an atomic ratio, preferably In/Zn is greater thanor equal to 1 and less than or equal to 20 in an atomic ratio, or morepreferably In/Zn is greater than or equal to 1.5 and less than or equalto 15 in an atomic ratio. When the atomic ratio of Zn is in the aboverange, the field effect mobility of the transistor can be improved.Here, when the atomic ratio of the compound is In:Zn:O=X:Y:Z, it ispreferable to satisfy the relation of Z>1.5X+Y.

For the oxide semiconductor layer, a thin film using a materialrepresented by the chemical formula, InMO₃(ZnO)_(m) (m>0), can be used.Here, M represents one or more metal elements selected from Ga, Al, Mn,and Co. For example, M can be Ga, Ga and Al, Ga and Mn, Ga and Co, orthe like.

As an oxide semiconductor, the band gap of the material is preferablygreater than or equal to 3 eV, more preferably greater than or equal to3 eV and less than 3.6 eV. In addition, the electron affinity of thematerial is preferably greater than or equal to 4 eV, more preferablygreater than or equal to 4 eV and less than 4.9 eV. Among suchmaterials, a material whose carrier concentration derived from a donoror an acceptor is preferably lower than 1×10¹⁴ cm⁻³, more preferablylower than 1×10¹¹ cm⁻³. Further, the hydrogen concentration in the oxidesemiconductor layer is lower than 1×10¹⁸ cm⁻³, preferably lower than1×10¹⁶ cm⁻³. The oxide semiconductor layer is i-type (intrinsic) bybeing highly purified. In a thin film transistor including the oxidesemiconductor layer as an active layer, the off-state current can takean extremely low value of 1 zA (zetoampere, 10⁻²¹ A)

The oxygen deficiency in the oxide semiconductor layer 106 and theinterface state between the base insulating layer 102 and the oxidesemiconductor layer 106 can be reduced when the oxide semiconductorlayer is in contact with the base insulating layer. By the reduction inthe interface state, fluctuation in the threshold voltage after the BTtest can be reduced.

It is preferable that the gate insulating layer 112 can have a structuresimilar to that of the base insulating layer 102 and be an insulatinglayer containing a silicon peroxide radical. At this time, a materialhaving a high dielectric constant, such as hafnium oxide or aluminumoxide, may be used for part of the gate insulating layer 112 inconsideration of the function of the gate insulating layer of thetransistor. Alternatively, a stacked layer of silicon oxide, siliconoxynitride, or silicon nitride and a material having a high dielectricconstant, such as hafnium oxide or aluminum oxide, may be used inconsideration of a gate withstand voltage, a condition of an interfacebetween the oxide semiconductor layer and the gate insulating layer 112,or the like. At this time, a layer of silicon oxide or siliconoxynitride is preferably formed on a side where the gate insulatinglayer 112 is in contact with the oxide semiconductor layer 106.

A protective insulating layer may further be provided over thetransistor 151. The protective insulating layer can have a structuresimilar to that of the base insulating layer 102. In order toelectrically connect the source electrode 108 a or the drain electrode108 b and a wiring, an opening may be formed in the base insulatinglayer 102, the gate insulating layer 112, and the like. A second gateelectrode may further be provided below the oxide semiconductor layer106. Note that it is not always necessary but preferable to process theoxide semiconductor layer 106 into an island shape.

FIGS. 2A to 2D illustrate cross-sectional structures of transistorshaving different structures from that of the transistor 151.

A transistor 152 in FIG. 2A is the same as the transistor 151 in that itincludes a base insulating layer 102, an oxide semiconductor layer 106,a source electrode 108 a, a drain electrode 108 b, a gate insulatinglayer 112, and a gate electrode 114. The differences between thetransistor 152 and the transistor 151 are the positions where the oxidesemiconductor layer 106 is connected to the source electrode 108 a andthe drain electrode 108 b. That is, in the transistor 152, the sourceelectrode 108 a and the drain electrode 108 b are in contact with bottomportions of the oxide semiconductor layer 106. The other components aresimilar to those of the transistor 151 in FIGS. 1A to 1C.

A transistor 153 in FIG. 2B is the same as the transistor 152 in that itincludes a base insulating layer 102, an oxide semiconductor layer 106,a source electrode 108 a, a drain electrode 108 b, a gate insulatinglayer 112, and a gate electrode 114. The difference between thetransistor 153 and the transistor 151 is the position of the gateelectrode with respect to the oxide semiconductor layer 106. That is, inthe transistor 153, the gate electrode is provided below the oxidesemiconductor layer 106 with the gate insulating layer 112 interposedtherebetween. In addition, in the transistor 153, a protectiveinsulating layer 124 is provided so as to cover the source electrode 108a, the drain electrode 108 b, and the oxide semiconductor layer 106. Theother components are similar to those of the transistor 152 in FIG. 2A.In the transistor 153, the gate insulating layer 112 and the protectiveinsulating layer 124 which are in contact with the oxide semiconductorlayer 106 are each formed using an insulating layer containing a siliconperoxide radical.

A transistor 154 in FIG. 2C is the same as the transistor 151 in that itincludes a base insulating layer 102, an oxide semiconductor layer 106,a source electrode 108 a, a drain electrode 108 b, a gate insulatinglayer 112, and a gate electrode 114. The difference between thetransistor 154 and the transistor 151 is the position of the gateelectrode with respect to the oxide semiconductor layer 106. That is, inthe transistor 154, the gate electrode is provided below the oxidesemiconductor layer 106 with the gate insulating layer 112 interposedtherebetween. In addition, in the transistor 154, a protectiveinsulating layer 124 is provided so as to cover the source electrode 108a, the drain electrode 108 b, and the oxide semiconductor layer 106. Theother components are similar to those of the transistor 151 in FIGS. 1Ato 1C. In the transistor 154, the gate insulating layer 112 and theprotective insulating layer 124 which are in contact with the oxidesemiconductor layer 106 are each formed using an insulating layercontaining a silicon peroxide radical.

A transistor 155 in FIG. 2D is the same as the transistor 151 and thetransistor 152 in that it includes a base insulating layer 102, a gateinsulating layer 112, a gate electrode 114, a source electrode 108 a,and a drain electrode 108 b. The transistor 155 is different from thetransistor 151 and the transistor 152 in that a channel region 126, asource region 122 a, and a drain region 122 b are formed in the oxidesemiconductor layer in the same plane. The source region 122 a and thedrain region 122 b are connected to the source electrode 108 a and thedrain electrode 108 b, respectively, through opening provided in aprotective insulating layer 124 interposed therebetween. Note that inFIG. 2D, the gate insulating layer 112 is provided only under the gateelectrode 114; however, one embodiment of the present invention is notlimited thereto. For example, the gate insulating layer 112 may beprovided so as to cover the oxide semiconductor layer including thechannel region 126, the source region 122 a, and the drain region 122 b.

Examples of a manufacturing process of the transistor in FIGS. 1A to 1Cwill be described below with reference to FIGS. 3A to 3E.

To begin with, an example of a manufacturing process of the transistor151 in FIGS. 1A to 1C will be described with reference to FIGS. 3A to3E.

First, a base insulating layer 102 is formed over a substrate 100 (seeFIG. 3A). In this embodiment, at least any one of insulating layers incontact with an oxide semiconductor layer, which include the baseinsulating layer 102, contains a silicon peroxide radical.

There is no particular limitation on the property of a material and thelike of the substrate 100 as long as the material has heat resistanceenough to withstand at least heat treatment to be performed later. Forexample, a glass substrate, a ceramic substrate, a quartz substrate, asapphire substrate, or the like can be used as the substrate 100.Alternatively, a single crystal semiconductor substrate or apolycrystalline semiconductor substrate made of silicon, siliconcarbide, or the like, a compound semiconductor substrate made of silicongermanium or the like, an SOI substrate, or the like may be used as thesubstrate 100. Still alternatively, any of these substrates furtherprovided with a semiconductor element may be used as the substrate 100.

A flexible substrate may be used as the substrate 100. In that case, atransistor can be formed directly on the flexible substrate. Note thatas a method for forming a transistor over a flexible substrate, there isalso a method in which, after a non-flexible substrate is used as thesubstrate 100 and a transistor is formed thereover, the transistor isseparated from the substrate and transferred to a flexible substrate. Inthat case, a separation layer is preferably provided between thesubstrate 100 and the transistor.

As a formation method of the base insulating layer 102, a plasma CVDmethod or a sputtering method can be employed, for example. The baseinsulating layer containing a silicon peroxide radical is preferablyformed by a sputtering method. As a material of the base insulatinglayer 102, silicon oxide, silicon oxynitride, or the like may be used.Alternatively, the base insulating layer 102 may be formed using astacked layer of the above material and silicon oxide, silicon nitride,silicon oxynitride, silicon nitride oxide, aluminum oxide, aluminumnitride, a mixed material of any of them, or the like. In the case wherethe base insulating layer 102 is formed to have a stacked-layerstructure, a layer of silicon oxide or silicon oxynitride is preferablyformed on a side where the base insulating layer 102 is in contact withthe oxide semiconductor layer 106. The total thickness of the baseinsulating layer 102 is preferably 20 nm or more, more preferably 100 nmor more. When the thick base insulating layer 102 is formed, the amountof silicon peroxide radicals of the base insulating layer 102 can beincreased.

In order to form the insulating layer containing a silicon peroxideradical by a sputtering method, in the case where oxygen or a mixed gasof oxygen and a rare gas (such as helium, neon, argon, krypton, orxenon) is used as a film formation gas, the proportion of oxygen ispreferably set higher. For example, the concentration of oxygen in thewhole gas is preferably set to be higher than or equal to 6% and lowerthan 100%.

For example, a silicon oxide film is formed by an RF sputtering methodunder the following conditions: quartz (preferably synthetic quartz) isused as a target; the substrate temperature is higher than or equal to30° C. and lower than or equal to 450° C. (preferably higher than orequal to 70° C. and lower than or equal to 200° C.); the distancebetween the substrate and the target (the T-S distance) is greater thanor equal to 20 mm and less than or equal to 400 mm (preferably greaterthan or equal to 40 mm and less than or equal to 200 mm); the pressureis higher than or equal to 0.1 Pa and lower than or equal to 4 Pa(preferably higher than or equal to 0.2 Pa and lower than or equal to1.2 Pa), the high-frequency power is higher than or equal to 0.5 kW andlower than or equal to 12 kW (preferably higher than or equal to 1 kWand lower than or equal to 5 kW); and the proportion of oxygen(O₂/(O₂+Ar)) in the film formation gas is higher than or equal to 1% andlower than or equal to 100% (preferably higher than or equal to 6% andlower than or equal to 100%). Note that a silicon target may be used asthe target instead of the quartz (preferably synthetic quartz) target.As the film formation gas, oxygen or a mixed gas of oxygen and argon isused.

Next, an oxide semiconductor layer is formed over the base insulatinglayer 102 and processed to form the oxide semiconductor layer 106 havingan island shape (see FIG. 3B).

For example, the oxide semiconductor layer can be formed by a sputteringmethod, a vacuum evaporation method, a pulse laser deposition method, aCVD method, or the like. The thickness of the oxide semiconductor layeris preferably greater than or equal to 3 nm and less than or equal to 50nm. This is because when the oxide semiconductor layer is too thick(e.g., 100 nm or more), there is a possibility that the short channeleffect might have a large influence and the transistor with small sizemight be normally on. Here, “normally on” means a state where a channelexists without application of a voltage to a gate electrode and acurrent flows through the transistor. Note that the base insulatinglayer 102 and the oxide semiconductor layer are preferably formedsuccessively without exposure to the air.

In this embodiment, the oxide semiconductor layer is formed by asputtering method using an In—Ga—Zn—O-based oxide target.

As the In—Ga—Zn—O-based oxide target, for example, an oxide targethaving a composition ratio of In₂O₃:Ga₂O₃:ZnO=1:1:1 [molar ratio] can beused. Note that it is not necessary to limit the material and thecomposition ratio of the target to the above. For example, an oxidetarget having a composition ratio of In₂O₃:Ga₂O₃:ZnO=1:1:2 [molar ratio]can also be used.

The relative density of the oxide target is higher than or equal to 90%and lower than or equal to 100%, preferably higher than or equal to 95%to lower than or equal 99.9%. This is because, with the use of the metaloxide target with a high relative density, the dense oxide semiconductorlayer can be formed.

The film formation may be performed under a rare gas atmosphere, anoxygen atmosphere, a mixed atmosphere containing a rare gas and oxygen,or the like. Moreover, it is preferably performed under an atmosphereusing a high-purity gas in which impurities such as hydrogen, water, ahydroxyl group, and hydride are sufficiently removed so that entry ofhydrogen, water, a hydroxyl group, and hydride into the oxidesemiconductor layer can be prevented.

The oxide semiconductor layer may be subjected to plasma treatmentcontaining oxygen. By performing plasma treatment containing oxygen onthe oxide semiconductor layer, the oxygen can be contained either orboth in the oxide semiconductor layer or/and in the vicinity of theinterface of the oxide semiconductor layer. In that case, the amount ofoxygen contained in the oxide semiconductor layer is greater than thestoichiometric proportion of the oxide semiconductor layer, preferablygreater than the stoichiometric proportion and less than the double ofthe stoichiometric proportion. Alternatively, the amount of oxygencontained may be greater than Y, preferably greater than Y and less than2Y, where the amount of oxygen contained in the case where a material ofthe oxide semiconductor layer is single crystal is Y. Stillalternatively, the amount of oxygen may be greater than Z, preferablygreater than Z and less than 2Z based on the amount of oxygen Z in theinsulating film in the case where oxygen plasma treatment is notperformed. The reason why the above preferable range has the upper limitis because the oxide semiconductor layer might absorb hydrogen, as ahydrogen absorbing alloy (a hydrogen storage alloy) does, when theamount of oxygen is too large. Note that in the oxide semiconductorlayer, the amount of oxygen is larger than the amount of hydrogen.

For example, the oxide semiconductor layer can be formed as follows.

An example of the film formation conditions is as follows: the distancebetween the substrate and the target is 60 mm; the pressure is 0.4 Pa;the direct-current (DC) power is 0.5 kW; and the film formationatmosphere is a mixed atmosphere containing argon and oxygen (the flowrate of the oxygen is 33%). Note that a pulse DC sputtering method ispreferable because powder substances (also referred to as particles ordust) generated in film formation can be reduced and the film thicknesscan be uniform.

First, the substrate 100 is placed in a film formation chamber keptunder reduced pressure, and the substrate temperature is set to atemperature higher than or equal to 100° C. and lower than or equal to600° C., preferably higher than or equal to 200° C. and lower than orequal to 400° C. The concentration of hydrogen (including water and acompound having a hydroxyl group) and other impurities in the oxidesemiconductor layer can be reduced when film formation is performedwhile the substrate 100 is heated. Moreover, damage due to sputteringcan be reduced. In addition, oxygen is released from the base insulatinglayer 102, whereby oxygen deficiency in the oxide semiconductor layerand an interface state between the base insulating layer 102 and theoxide semiconductor layer can be reduced.

Note that before the oxide semiconductor layer 106 is formed by asputtering method, a substance attached to a surface where the oxidesemiconductor layer is to be formed (e.g., a surface of the baseinsulating layer 102) may be removed by reverse sputtering in which arare gas is introduced and plasma is generated. Here, the reversesputtering is a method by which ions collide with a surface to beprocessed so that the surface is modified, in contrast to normalsputtering by which ions collide with a sputtering target. An example ofa method for making ions collide with a surface to be processed is amethod in which a high-frequency voltage is applied to the surface sideunder an argon atmosphere so that plasma is generated near an object tobe processed. Note that an atmosphere of nitrogen, helium, oxygen, orthe like may be used instead of an argon atmosphere.

The oxide semiconductor layer 106 can be processed by etching after amask having a desired shape is formed over the oxide semiconductorlayer. The mask can be formed by a method such as photolithography.Alternatively, the mask may be formed by an ink-jet method or the like.

For the etching of the oxide semiconductor layer, either wet etching ordry etching may be employed. It is needless to say that both of them maybe employed in combination.

After that, heat treatment (first heat treatment) is preferablyperformed on the oxide semiconductor layer. By the first heat treatment,hydrogen (including water and a compound having a hydroxyl group) in theoxide semiconductor layer can be removed and a structure of the oxidesemiconductor layer can be ordered. The temperature of the first heattreatment is higher than or equal to 100° C. and lower than or equal to650° C. or lower than the strain point of the substrate, preferablyhigher than or equal to 250° C. and lower than or equal to 600° C. Theatmosphere of the first heat treatment is an oxidizing gas atmosphere oran inert gas atmosphere.

Note that an inert gas is a gas that contains nitrogen or a rare gas asits main component and, preferably, does not contain water, hydrogen,and the like. For example, the purity of nitrogen or a rare gas such ashelium, neon, or argon introduced into a heat treatment apparatus is setto 6N (99.9999%) or higher, preferably 7N (99.99999%) or higher (i.e.,the impurity concentration is 1 ppm or lower, preferably 0.1 ppm orlower). An inert gas atmosphere is an atmosphere that contains an inertgas as its main component and contains a reactive gas of 10 ppm orlower. The reactive gas is a gas that reacts with a semiconductor,metal, or the like.

Note that the oxidizing gas is oxygen, ozone, nitrous oxide, or thelike, and it is preferable that the oxidizing gas does not containwater, hydrogen, and the like. For example, the purity of oxygen, ozone,or nitrous oxide introduced into a heat treatment apparatus is set to 6N(99.9999%) or higher, preferably 7N (99.99999%) or higher (i.e., theimpurity concentration is 1 ppm or lower, preferably 0.1 ppm or lower).As the oxidizing gas atmosphere, an atmosphere in which an oxidizing gasis mixed with an inert gas may be used, and the oxidizing gas of atleast 10 ppm is contained.

By the first heat treatment, oxygen is released from the base insulatinglayer 102, whereby the oxygen deficiency in the oxide semiconductorlayer 106 and the interface state between the base insulating layer 102and the oxide semiconductor layer 106 can be reduced. By the abovereduction in the interface state, the fluctuation in the thresholdvoltage before and after a BT test can be reduced. Further, in general,it is known that the oxygen deficiency in the oxide semiconductor layerbecomes donors and the source for generating electrons which arecarriers. By the generation of electrons in the oxide semiconductorlayer 106, the threshold voltage of the transistor 151 is shifted in anegative direction, so that the transistor 151 tends to be normally on.By embedding the oxygen deficiency in the oxide semiconductor layer 106,the shift of the threshold voltage in a negative direction can besuppressed.

The heat treatment can be performed in such a manner that, for example,an object to be processed is introduced into an electric furnace inwhich a resistance heating element or the like is used and heated at350° C. under a nitrogen atmosphere for an hour. During the heattreatment, the oxide semiconductor layer is not exposed to the air toprevent the entry of water and hydrogen.

Note that a heat treatment apparatus is not limited to an electricfurnace, and may include a device for heating an object to be processedby heat conduction or heat radiation from a medium such as a heated gas.For example, a rapid thermal anneal (RTA) apparatus such as a gas rapidthermal anneal (GRTA) apparatus or a lamp rapid thermal anneal (LRTA)apparatus can be used. An LRTA apparatus is an apparatus for heating anobject to be processed by radiation of light (electromagnetic waves)emitted from a lamp such as a halogen lamp, a metal halide lamp, a xenonarc lamp, a carbon arc lamp, a high-pressure sodium lamp, or ahigh-pressure mercury lamp. A GRTA apparatus is an apparatus for heattreatment using a high temperature gas. As the high temperature gas,used is an inert gas which does not react with an object to be processedin heat treatment, for example, nitrogen or a rare gas such as argon.

For example, as the first heat treatment, GRTA treatment may beperformed as follows. The object to be processed is put in an inert gasatmosphere that has been heated, heated for several minutes, and thentaken out of the inert gas atmosphere. GRTA treatment enableshigh-temperature heat treatment in a short time. Moreover, GRTAtreatment can be employed even when the temperature exceeds the uppertemperature limit of the object to be processed. Note that the inert gasatmosphere may be switched to an atmosphere containing an oxidizing gasduring the treatment. This is because by performing the first heattreatment under an atmosphere containing the oxidizing gas, oxygendeficiency in the oxide semiconductor layer 106 can be embedded anddefect levels in an energy gap due to the oxygen deficiency can bereduced.

The above heat treatment (first heat treatment) can also be referred toas dehydration treatment, dehydrogenation treatment, or the like becauseof its advantageous effect of removing hydrogen (including water and acompound having a hydroxyl group) and the like. In addition, the aboveheat treatment can also be referred to as treatment for supplying oxygenbecause of its advantageous effect of supplying oxygen from theinsulating layer, a heat treatment atmosphere, or the like. Thedehydration treatment, dehydrogenation treatment, or treatment forsupplying oxygen may be performed at the timing, for example, after theoxide semiconductor layer is processed to have an island shape. Suchdehydration treatment, dehydrogenation treatment, or treatment forsupplying oxygen may be performed once or plural times.

Note that the case is described here where the first heat treatment isperformed after the oxide semiconductor layer 106 is processed to havean island shape; however, one embodiment of the present invention is notlimited thereto. The oxide semiconductor layer 106 may be processedafter the first heat treatment.

Next, a conductive layer for forming the source electrode and the drainelectrode (including a wiring formed in the same layer as the sourceelectrode and the drain electrode) is formed over the base insulatinglayer 102 and the oxide semiconductor layer 106 and processed to formthe source electrode 108 a and the drain electrode 108 b (see FIG. 3C).The channel length L of the transistor depends on the minimum distancebetween the edges of the source electrode 108 a and the drain electrode108 b which are formed here.

As the conductive layer used for the source electrode 108 a and thedrain electrode 108 b, for example, a metal layer containing an elementselected from Al, Cr, Cu, Ta, Ti, Mo, and W, or a metal nitride layercontaining any of the above elements as its component (e.g., a titaniumnitride layer, a molybdenum nitride layer, or a tungsten nitride layer)can be used. A high melting point metal layer of Ti, Mo, W, or the likeor a metal nitride layer of any of these elements (a titanium nitridelayer, a molybdenum nitride layer, or a tungsten nitride layer) may bestacked on one of or both a bottom side and a top side of a low meltingpoint and low resistance metal layer of Al, Cu, or the like.

Alternatively, the conductive layer used for the source electrode 108 aand the drain electrode 108 b may be formed using a conductive metaloxide. As the conductive metal oxide, an indium oxide, a tin oxide, azinc oxide, an indium oxide-tin oxide mixed oxide (abbreviated to ITO),an indium oxide-zinc oxide mixed oxide, or any of these metal oxidematerials containing a silicon oxide can be used.

The conductive layer can be processed by etching with the use of aresist mask. Ultraviolet, KrF laser light, ArF laser light, or the likeis preferably used for light exposure for forming a resist mask for theetching.

In the case where light exposure is performed so that the channel lengthL is less than 25 nm, the light exposure at the time of forming theresist mask is preferably performed using, for example, extremeultraviolet having an extremely short wavelength of several nanometersto several tens of nanometers. In the light exposure using extremeultraviolet, the resolution is high and the focus depth is large. Thus,the channel length L of the transistor formed later can be reduced,whereby the operation speed of a circuit can be increased.

Etching may be performed with the use of a resist mask formed using aso-called multi-tone mask. A resist mask formed using a multi-tone maskhas a plurality of thicknesses and can be further changed in shape byashing; thus, such a resist mask can be used in a plurality of etchingsteps for different patterns. Therefore, a resist mask for at least twokinds of patterns can be formed using a multi-tone mask, resulting insimplification of the process.

Note that in etching of the conductive layer, part of the oxidesemiconductor layer 106 is etched, so that the oxide semiconductor layerhaving a groove (a recessed portion) is formed in some cases.

After that, by plasma treatment using a gas such as oxygen, ozone, ornitrous oxide, a surface of an exposed portion of the oxidesemiconductor layer 106 may be oxidized and oxygen deficiency may beembedded. In the case where plasma treatment is performed, the gateinsulating layer 112 which is to be in contact with part of the oxidesemiconductor layer 106 is preferably formed without being exposed tothe air, following the plasma treatment.

Next, the gate insulating layer 112 is formed so as to cover the sourceelectrode 108 a and the drain electrode 108 b and to be in contact withpart of the oxide semiconductor layer 106 (see FIG. 3D).

The gate insulating layer 112 can have a structure similar to that ofthe base insulating layer 102. Note that a material having a highdielectric constant, such as hafnium oxide or aluminum oxide, may beused for part of the gate insulating layer 112 in consideration of thefunction of the gate insulating layer of the transistor. Alternatively,a stacked layer of silicon oxide, silicon oxynitride, or silicon nitrideand a material having a high dielectric constant, such as hafnium oxideor aluminum oxide, may be used in consideration of a gate withstandvoltage, a condition of an interface between the oxide semiconductorlayer and the gate insulating layer 112, or the like. The totalthickness of the gate insulating layer 112 is preferably greater than orequal to 1 nm and less than or equal to 300 nm, more preferably greaterthan or equal to 5 nm and less than or equal to 50 nm. The larger thethickness of the gate insulating layer is, the more easily a shortchannel effect occurs; thus, the threshold voltage tends to shift to anegative direction. In addition, it is found that when the thickness ofthe gate insulating layer is less than or equal to 5 nm, leakage due toa tunnel current is increased. At least any one of the insulating layersin contact with the oxide semiconductor layer, which include the gateinsulating layer 112, contains a silicon peroxide radical.

Second heat treatment is preferably performed after the gate insulatinglayer 112 is formed. The second heat treatment is performed at atemperature of higher than or equal to 250° C. and lower than or equalto 700° C., preferably higher than or equal to 350° C. and lower than orequal to 600° C. or lower than the strain point of the substrate.

The second heat treatment may be performed under an atmosphere of anoxidizing gas or an inert gas. Note that it is preferable that water,hydrogen, and the like be not contained in the atmosphere of oxidizinggas or an inert gas. Further, the purity of the gas introduced into aheat treatment apparatus is preferably set to 6N (99.9999%) or higher,more preferably 7N (99.99999%) or higher (that is, the impurityconcentration is 1 ppm or lower, preferably 0.1 ppm or lower).

The second heat treatment is performed while the oxide semiconductorlayer 106 and the gate insulating layer 112 are in contact with eachother. Thus, oxygen which is one of main components of the oxidesemiconductor can be supplied from the gate insulating layer 112containing a silicon peroxide radical to the oxide semiconductor layer106. Accordingly, oxygen deficiency in the oxide semiconductor layer 106and an interface state between the oxide semiconductor layer and thegate insulating layer 112 can be reduced. At the same time, deficiencyin the gate insulating layer 112 can also be reduced.

Note that there is no particular limitation on the timing of the secondheat treatment as long as it is after the gate insulating layer 112 isformed. For example, the second heat treatment may be performed afterthe gate electrode 114 is formed.

Then, the gate electrode 114 is formed (see FIG. 3E). The gate electrode114 can be formed using a metal material such as molybdenum, titanium,tantalum, tungsten, aluminum, copper, neodymium, or scandium, nitride ofany of these metal materials, or an alloy material which contains any ofthese metal materials as its main component. Note that the gateelectrode 114 may have a single-layer structure or a stacked-layerstructure.

Through the above process, the transistor 151 is formed.

Next, an example of a manufacturing process of the transistor 152 inFIG. 2A will be described with reference to FIGS. 4A to 4E.

First, a base insulating layer 102 is formed over a substrate 100 (seeFIG. 4A). At least any one of the insulating layers in contact with theoxide semiconductor layer, which include the base insulating layer 102,contains a silicon peroxide radical.

Next, a conductive layer for forming the source electrode and the drainelectrode (including a wiring formed in the same layer as the sourceelectrode and the drain electrode) is formed over the base insulatinglayer 102 and processed to form a source electrode 108 a and a drainelectrode 108 b (see FIG. 4B). After that, second heat treatment similarto that performed on the transistor 151 may be performed.

Next, an oxide semiconductor layer is formed over the base insulatinglayer 102 so as to be connected to the source electrode 108 a and thedrain electrode 108 b and processed to form an oxide semiconductor layer106 having an island shape (see FIG. 4C). After that, first heattreatment similar to that performed on the transistor 151 may beperformed.

Next, a gate insulating layer 112 is formed so as to be in contact withthe oxide semiconductor layer 106 and part of the source electrode 108 aand the drain electrode 108 b and cover the source electrode 108 a, thedrain electrode 108 b, and the oxide semiconductor layer 106 (see FIG.4D). At least any one of the insulating layers in contact with the oxidesemiconductor layer, which include the gate insulating layer 112,contains a silicon peroxide radical. After that, second heat treatmentsimilar to that performed on the transistor 151 may be performed.

Then, a gate electrode 114 is formed (see FIG. 4E).

Through the above process, the transistor 152 is formed.

When a charge is trapped at the surface of the oxide semiconductorlayer, the threshold voltage of the transistor is shifted. For example,when a positive charge is trapped on the back channel side, thethreshold voltage of the transistor is shifted in a negative direction.However, as one of factors of such charge trapping, the model wherecations (or atoms which are sources of the cations) travel and aretrapped can be supposed. In one embodiment of the present invention, theinterface states between the oxide semiconductor layer and the baseinsulating layer 102 and between the oxide semiconductor layer and thegate insulating layer 112 are reduced by the base insulating layer 102and the gate insulating layer 112 which each contain a silicon peroxideradical, so that it is possible to reduce charge trapping which may becaused in the above model; therefore, the shift of the threshold voltageof the transistor can be suppressed.

Next, an example of a manufacturing process of the transistor 153 inFIG. 2B will be described with reference to FIGS. 5A to 5E.

First, a base insulating layer 102 is formed over a substrate 100 (seeFIG. 5A).

Next, a gate electrode 114 is formed over the base insulating layer 102(see FIG. 5B).

Next, a gate insulating layer 112 is formed over the gate electrode 114.At least any one of the insulating layers in contact with the oxidesemiconductor layer, which include the gate insulating layer 112,contains a silicon peroxide radical (see FIG. 5C).

Next, a source electrode 108 a and a drain electrode 108 b are formedover the gate insulating layer 112, an oxide semiconductor layer isformed so as to be connected to the source electrode 108 a and the drainelectrode 108 b, and the oxide semiconductor layer is processed to forman oxide semiconductor layer 106 having an island shape (see FIG. 5D).After that, first heat treatment similar to that performed on thetransistor 151 may be performed. After that, second heat treatmentsimilar to that performed on the transistor 151 may be performed.

Next, a protective insulating layer 124 is formed so as to cover theoxide semiconductor layer 106, the source electrode 108 a, and the drainelectrode 108 b (see FIG. 5E). At least any one of the insulating layersin contact with the oxide semiconductor layer, which include theprotective insulating layer 124, contains a silicon peroxide radical.

Through the above process, the transistor 153 is formed.

Next, an example of a manufacturing process of the transistor 154 inFIG. 2C will be described with reference to FIGS. 6A to 6E.

First, a base insulating layer 102 is formed over a substrate 100 (seeFIG. 6A).

Next, a gate electrode 114 is formed over the base insulating layer 102(see FIG. 6B).

Next, a gate insulating layer 112 is formed over the gate electrode 114(see FIG. 6C). At least any one of the insulating layers in contact withthe oxide semiconductor layer, which include the gate insulating layer112, contains a silicon peroxide radical.

Next, an oxide semiconductor layer is formed over the gate insulatinglayer 112 and processed to form an oxide semiconductor layer 106 havingan island shape. After that, first heat treatment similar to thatperformed on the transistor 151 may be performed. Then, a sourceelectrode 108 a and a drain electrode 108 b are connected to the oxidesemiconductor layer 106 (see FIG. 6D).

Next, a protective insulating layer 124 is formed so as to cover theoxide semiconductor layer 106, the source electrode 108 a, and the drainelectrode 108 b (see FIG. 6E). At least any one of the insulating layersin contact with the oxide semiconductor layer, which include theprotective insulating layer 124, contains a silicon peroxide radical.

Through the above process, the transistor 154 is formed.

Next, an example of a manufacturing process of the transistor 155 inFIG. 2D will be described with reference to FIGS. 7A to 7E.

First, a base insulating layer 102 is formed over a substrate 100 (seeFIG. 7A). At least any one of the insulating layers in contact with theoxide semiconductor layer, which include the base insulating layer 102,contains a silicon peroxide radical.

Next, an oxide semiconductor layer is formed over the base insulatinglayer 102 and processed to form an oxide semiconductor layer 106 havingan island shape (see FIG. 7B). After that, first heat treatment similarto that performed on the transistor 151 may be performed.

Next, a gate insulating layer 112 and a gate electrode 114 are formedand processed to have similar patterns by photolithography (see FIG.7C). At this time, after the process of the gate electrode 114, the gateinsulating layer 112 may be processed using the gate electrode 114 as amask.

Next, the resistance of the oxide semiconductor layer 106 is reducedusing the gate electrode 114 as a mask, so that a source region 122 aand a drain region 122 b are formed. A region under the gate electrodewhere the resistance is not reduced becomes a channel region 126 (seeFIG. 7D). At this time, a channel length L of the transistor isdetermined by the width of the gate electrode. By patterning using thegate electrode as the mask in such a manner, the source region and thedrain region do not overlap with the gate electrode and parasiticcapacitance is not generated; therefore, the operation speed of thetransistor can be increased.

Next, a protective insulating layer 124 is formed and openings areprovided in regions of the protective insulating layer 124, whichoverlap with the source region 122 a and the drain region 122 b. Aconductive layer for forming the source electrode and the drainelectrode (including a wiring formed in the same layer as the source anddrain electrodes) is formed and processed to form a source electrode 108a and a drain electrode 108 b (see FIG. 7E).

Through the above process, the transistor 155 is formed.

The oxide semiconductor layer used as the active layer of the transistordescribed in this embodiment is an oxide semiconductor layer highlypurified to be i-type (intrinsic), through substrate heating information of an oxide semiconductor layer or heat treatment afterformation of the oxide semiconductor layer, in which impurities such ashydrogen (including water and a compound having a hydroxyl group) areremoved from the oxide semiconductor and oxygen which is one of maincomponents of the oxide semiconductor and is simultaneously reduced in astep of removing impurities is supplied to the oxide semiconductor layerfrom an insulating layer containing a silicon peroxide radical. Thetransistor including the oxide semiconductor film which is highlypurified in such a manner has a small off-state current, suppressedvariation in the electrical characteristics, and electric stability.

Thus, a semiconductor device including an oxide semiconductor and havingstable electric characteristics can be provided. Therefore, asemiconductor device with high reliability can be provided.

The structures, the methods, and the like described in this embodimentcan be combined as appropriate with any of the structures, the methods,and the like described in the other embodiments.

[Embodiment 2]

A semiconductor device (also referred to as a display device) with adisplay function can be manufactured using the transistor, an example ofwhich is shown in Embodiment 1. Some or all driver circuits includingthe transistors can be formed over a substrate where a pixel portion isformed, whereby a system-on-panel can be obtained.

In FIG. 8A, a sealant 205 is provided to surround a pixel portion 202provided over a first substrate 201, and the pixel portion 202 is sealedwith the sealant 205 between the first substrate 201 and a secondsubstrate 206. In FIG. 8A, a scan line driver circuit 204 and a signalline driver circuit 203 each are formed using a single crystalsemiconductor layer or a polycrystalline semiconductor layer over asubstrate prepared separately, and mounted in a region different fromthe region surrounded by the sealant 205 over the first substrate 201.Various signals and potentials are supplied to the signal line drivercircuit 203 and the scan line driver circuit 204, each of which isseparately formed, and the pixel portion 202, from flexible printedcircuits (FPCs) 218 a and 218 b.

In FIGS. 8B and 8C, the sealant 205 is provided to surround the pixelportion 202 and the scan line driver circuit 204 which are provided overthe first substrate 201. The second substrate 206 is provided over thepixel portion 202 and the scan line driver circuit 204. Thus, the pixelportion 202 and the scan line driver circuit 204 are sealed togetherwith a display element, by the first substrate 201, the sealant 205, andthe second substrate 206. In FIGS. 8B and 8C, the signal line drivercircuit 203 is formed using a single crystal semiconductor layer or apolycrystalline semiconductor layer over a substrate preparedseparately, and mounted in a region different from the region surroundedby the sealant 205 over the first substrate 201. In FIGS. 8B and 8C,various signals and potentials are supplied to the signal line drivercircuit 203 which is separately formed, the scan line driver circuit204, and the pixel portion 202, from an FPC 218.

Although FIGS. 8B and 8C each show the example in which the signal linedriver circuit 203 is formed separately and mounted on the firstsubstrate 201, one embodiment of the present invention is not limited tothis structure. The scan line driver circuit may be separately formedand then mounted, or only part of the signal line driver circuit or partof the scan line driver circuit may be separately formed and thenmounted.

Note that a method for connecting a separately formed driver circuit isnot particularly limited, and a chip on glass (COG) method, a wirebonding method, a tape automated bonding (TAB) method, or the like canbe used. FIG. 8A shows an example in which the signal line drivercircuit 203 and the scan line driver circuit 204 are mounted by a COGmethod. FIG. 8B shows an example in which the signal line driver circuit203 is mounted by a COG method. FIG. 8C shows an example in which thesignal line driver circuit 203 is mounted by a TAB method.

The display device includes in its category a panel in which a displayelement is sealed and a module in which an IC such as a controller ismounted on the panel.

Note that a display device in this specification means an image displaydevice, a display device, or a light source (including a lightingdevice). The display device also includes the following modules in itscategory: a module to which a connector such as an FPC, a TAB tape, or atape carrier package (TCP) is attached; a module having a TAB tape or aTCP at the tip of which a printed wiring board is provided; and a modulein which an integrated circuit (IC) is directly mounted on a displayelement by a COG method.

The pixel portion and the scan line driver circuit provided over thefirst substrate include a plurality of transistors, and any oftransistors which are described in Embodiment 1 as the examples can beapplied.

As the display element provided in the display device, a liquid crystalelement (also referred to as a liquid crystal display element) or alight-emitting element (also referred to as a light-emitting displayelement) can be used. The light-emitting element includes, in itscategory, an element whose luminance is controlled by a current or avoltage, and specifically includes, in its category, an inorganicelectroluminescent (EL) element, an organic EL element, and the like.Furthermore, a display medium whose contrast is changed by an electriceffect, such as electronic ink, can also be used.

One embodiment of the semiconductor device is described with referenceto FIG. 9, FIG. 10, and FIG. 11. FIG. 9, FIG. 10, and FIG. 11 correspondto cross-sectional views taken along line M-N in FIG. 8B.

As illustrated in FIG. 9, FIG. 10, and FIG. 11, the semiconductor deviceincludes a connection terminal electrode 215 and a terminal electrode216. The connection terminal electrode 215 and the terminal electrode216 are electrically connected to a terminal included in the FPC 218through an anisotropic conductive layer 219.

The connection terminal electrode 215 is formed of the same conductivelayer as a first electrode layer 230. The terminal electrode 216 isformed of the same conductive layer as a source electrode and a drainelectrode of a transistor 210 and a transistor 211.

Each of the pixel portion 202 and the scan line driver circuit 204provided over the first substrate 201 includes a plurality oftransistors. In FIG. 9, FIG. 10, and FIG. 11, the transistor 210included in the pixel portion 202 and the transistor 211 included in thescan line driver circuit 204 are illustrated as an example.

In this embodiment, any of the transistors described in Embodiment 1 canbe applied to the transistors 210 and 211. Fluctuation in the electriccharacteristics of the transistors 210 and 211 is suppressed and thetransistors 210 and 211 are electrically stable. As described above, asemiconductor device with high reliability can be provided as thesemiconductor devices in this embodiment in FIG. 9, FIG. 10, and FIG.11.

The transistor 210 provided in the pixel portion 202 is electricallyconnected to the display element to form a display panel. A variety ofdisplay elements can be used as the display element as long as displaycan be performed.

FIG. 9 shows an example of a liquid crystal display device using aliquid crystal element as a display element. In FIG. 9, a liquid crystalelement 213 is a display element including the first electrode layer230, a second electrode layer 231, and a liquid crystal layer 208. Notethat insulating layers 232 and 233 serving as alignment layers areprovided so that the liquid crystal layer 208 is interposedtherebetween. The second electrode layer 231 is formed on the secondsubstrate 206 side. The first electrode layer 230 and the secondelectrode layer 231 are stacked with the liquid crystal layer 208interposed therebetween.

A spacer 235 is a columnar spacer obtained by selective etching of aninsulating layer and is provided in order to control the thickness (acell gap) of the liquid crystal layer 208. Alternatively, a sphericalspacer may be used.

In the case where a liquid crystal element is used as the displayelement, a thermotropic liquid crystal, a low-molecular liquid crystal,a high-molecular liquid crystal, a polymer dispersed liquid crystal, aferroelectric liquid crystal, an anti-ferroelectric liquid crystal, orthe like can be used. Such a liquid crystal material exhibits acholesteric phase, a smectic phase, a cubic phase, a chiral nematicphase, an isotropic phase, or the like depending on conditions.

Alternatively, a liquid crystal exhibiting a blue phase for which analignment layer is unnecessary may be used. A blue phase is one ofliquid crystal phases, which is generated just before a cholestericphase changes into an isotropic phase while temperature of cholestericliquid crystal is increased. Since the blue phase appears only in anarrow temperature range, a liquid crystal composition in which a chiralmaterial is mixed is used for the liquid crystal layer in order toimprove the temperature range. The liquid crystal composition whichincludes a liquid crystal exhibiting a blue phase and a chiral agent hasa short response time of 1 msec or less, has optical isotropy, whichmakes the alignment process unneeded, and has a small viewing angledependence. In addition, since an alignment layer does not need to beprovided and rubbing treatment is unnecessary, electrostatic dischargedamage caused by the rubbing treatment can be prevented and defects anddamage of the liquid crystal display device can be reduced in themanufacturing process. Thus, productivity of the liquid crystal displaydevice can be improved.

The specific resistivity of the liquid crystal material is 1×10⁹ Ω·cm ormore, preferably 1×10¹¹ Ω·cm or more, or more preferably 1×10¹² Ω·cm ormore. Note that the specific resistivity in this specification ismeasured at 20° C.

The size of a storage capacitor provided in the liquid crystal displaydevice is set in consideration of the leakage current of the transistorprovided in the pixel portion or the like so that a charge can be heldfor a predetermined period. Since the transistor including a highlypurified oxide semiconductor layer is used, a storage capacitor havingcapacitance which is ⅓ or less, preferably ⅕ or less with respect to aliquid crystal capacitance of each pixel is sufficient to be provided.

In the transistor used in this embodiment, which includes a highlypurified oxide semiconductor layer, the current in an off state (anoff-state current) can be made small. Therefore, an electrical signalsuch as an image signal can be held for a long period, and a writinginterval can be set long. Accordingly, frequency of refresh operationcan be reduced, which leads to an advantageous effect of suppressingpower consumption.

The field-effect mobility of the transistor including a highly purifiedoxide semiconductor layer used in this embodiment can be relativelyhigh, whereby high-speed operation is possible. Thus, by using thetransistor in a pixel portion of the liquid crystal display device, ahigh-quality image can be provided. In addition, since the transistorscan be separately provided in a driver circuit portion and a pixelportion over one substrate, the number of components of the liquidcrystal display device can be reduced.

For the liquid crystal display device, a twisted nematic (TN) mode, anin-plane-switching (IPS) mode, a fringe field switching (FFS) mode, anaxially symmetric aligned micro-cell (ASM) mode, an optical compensatedbirefringence (OCB) mode, a ferroelectric liquid crystal (FLC) mode, anantiferroelectric liquid crystal (AFLC) mode, or the like can be used.

A normally black liquid crystal display device such as a transmissiveliquid crystal display device utilizing a vertical alignment (VA) modeis preferable. The vertical alignment mode is one of methods ofcontrolling alignment of liquid crystal molecules of a liquid crystaldisplay panel. The vertical alignment mode is a mode in which liquidcrystal molecules are aligned vertically to a panel surface when avoltage is not applied. Some examples are given as the verticalalignment mode. For example, a multi-domain vertical alignment (MVA)mode, a patterned vertical alignment (PVA) mode, an ASV mode, and thelike can be given. Moreover, it is possible to use a method calleddomain multiplication or multi-domain design, in which a pixel isdivided into some regions (subpixels) and molecules are aligned indifferent directions in their respective regions.

In the display device, a black matrix (a light-blocking layer); anoptical member (an optical substrate) such as a polarizing member, aretardation member, or an anti-reflection member; and the like areprovided as appropriate. For example, circular polarization may beemployed by using a polarizing substrate and a retardation substrate. Inaddition, a backlight, a side light, or the like may be used as a lightsource.

In addition, with the use of a plurality of light-emitting diodes (LEDs)as a backlight, a time-division display method (a field-sequentialdriving method) can be employed. With the field-sequential drivingmethod, color display can be performed without using a color filter.

As a display method in the pixel portion, a progressive method, aninterlace method, or the like can be employed. Color elements controlledin a pixel at the time of color display are not limited to three colors:R, G, and B (R, G, and B correspond to red, green, and bluerespectively). For example, R, G, B, and W (W corresponds to white), orR, G, B, and one or more of yellow, cyan, magenta, and the like can beused. The sizes of display regions may be different between respectivedots of color elements. Note that the present invention is not limitedto the application to a display device for color display but can also beapplied to a display device for monochrome display.

Alternatively, as the display element included in the display device, alight-emitting element utilizing EL can be used. Light-emitting elementsutilizing EL are categorized by whether a light-emitting material is anorganic compound or an inorganic compound, and in general, the former iscalled an organic EL element and the latter is called an inorganic ELelement.

In an organic EL element, by application of a voltage to alight-emitting element, electrons and holes are separately injected froma pair of electrodes into a layer containing a light-emitting organiccompound, and current flows. The carriers (electrons and holes) arerecombined, and thus the light-emitting organic compound is excited. Thelight-emitting organic compound returns to a ground state from theexcited state, thereby emitting light. Owing to such a mechanism, such alight-emitting element is referred to as a current-excitationlight-emitting element.

The inorganic EL elements are classified according to their elementstructures into a dispersion-type inorganic EL element and a thin-filminorganic EL element. A dispersion-type inorganic EL element has alight-emitting layer where particles of a light-emitting material aredispersed in a binder, and its light emission mechanism isdonor-acceptor recombination type light emission that utilizes a donorlevel and an acceptor level. A thin-film inorganic EL element has astructure where a light-emitting layer is sandwiched between dielectriclayers, which are further sandwiched between electrodes, and its lightemission mechanism is localized type light emission that utilizesinner-shell electron transition of metal ions. Note that an example ofan organic EL element is described here as a light-emitting element.

In order to extract light emitted from the light-emitting element, atleast one of a pair of electrodes may be transparent. Then, a transistorand a light-emitting element are formed over a substrate. Thelight-emitting element can have any of the following structure: a topemission structure in which light is extracted from one surface side ofthe substrate where the transistor and the light-emitting element areprovided; a bottom emission structure in which light is extracted fromone surface side of the substrate where the transistor and thelight-emitting element are not provided; or a dual emission structure inwhich light is extracted from one surface side of the substrate wherethe transistor and the light-emitting element are provided and anothersurface side of the substrate where the transistor and thelight-emitting element are not provided.

FIG. 10 shows an example of a light-emitting device using alight-emitting element as a display element. A light-emitting element243 which is a display element is electrically connected to thetransistor 210 provided in the pixel portion 202. The structure of thelight-emitting element 243 is not limited to the stacked-layer structureincluding the first electrode layer 230, an electroluminescent layer241, and the second electrode layer 231, which is illustrated in FIG.10. The structure of the light-emitting element 243 can be changed asappropriate depending on a direction in which light is extracted fromthe light-emitting element 243, or the like.

A partition wall 240 can be formed using an organic insulating materialor an inorganic insulating material. It is particularly preferable thatthe partition wall 240 be formed using a photosensitive resin materialto have an opening over the first electrode layer 230 so that a sidewallof the opening is formed as a tilted surface with continuous curvature.

The electroluminescent layer 241 may be formed with either a singlelayer or a stacked layer of a plurality of layers.

A protective layer may be formed over the second electrode layer 231 andthe partition wall 240 in order to prevent entry of oxygen, hydrogen,moisture, carbon dioxide, or the like into the light-emitting element243. As the protective layer, a silicon nitride layer, a silicon nitrideoxide layer, a diamond-like carbon (DLC) layer, an aluminum oxide layer,an aluminum nitride layer, or the like can be formed. In a space sealedwith the first substrate 201, the second substrate 206, and the sealant205, a filler 244 is provided and tightly sealed. In such a manner, itis preferable that the light-emitting element be packaged (sealed) witha protective film (such as a laminate film or an ultraviolet curableresin film) or a cover material with high air-tightness and littledegasification so that the light-emitting element is not exposed to theoutside air.

As the filler 244, an ultraviolet curable resin or a thermosetting resincan be used in addition to an inert gas such as nitrogen or argon, andpolyvinyl chloride (PVC), an acrylic resin, a polyimide resin, an epoxyresin, a silicone resin, polyvinyl butyral (PVB), ethylene vinyl acetate(EVA), or the like can be used. For example, nitrogen may be used forthe filler.

If needed, an optical film, such as a polarizing plate, a circularlypolarizing plate (including an elliptically polarizing plate), aretardation plate (a quarter-wave plate or a half-wave plate), or acolor filter, may be provided as appropriate on a light-emitting surfaceof the light-emitting element. Further, the polarizing plate or thecircularly polarizing plate may be provided with an anti-reflectionlayer. For example, anti-glare treatment by which reflected light can bediffused by projections and depressions on the surface so as to reducethe glare can be performed.

Further, an electronic paper in which electronic ink is driven can beprovided as the display device. The electronic paper is also called anelectrophoretic display device (an electrophoretic display) and isadvantageous in that it has the same level of readability as regularpaper, it has less power consumption than other display devices, and itcan be made thin and light.

An electrophoretic display device can have various modes. Anelectrophoretic display device contains a plurality of microcapsulesdispersed in a solvent or a solute, each microcapsule containing firstparticles which are positively charged and second particles which arenegatively charged. By applying an electric field to the microcapsules,the particles in the microcapsules move in opposite directions to eachother and only the color of the particles gathering on one side isdisplayed. Note that the first particles and the second particles eachcontain pigment and do not move without an electric field. Moreover, thefirst particles and the second particles have different colors (whichmay be colorless) from each other.

Thus, an electrophoretic display device is a display that utilizes aso-called dielectrophoretic effect by which a substance having a highdielectric constant moves to a high-electric field region.

A solution in which the above microcapsules are dispersed in a solventis referred to as electronic ink. This electronic ink can be printed ona surface of glass, plastic, cloth, paper, or the like. Furthermore, byusing a color filter or particles that have a pigment, color display canalso be achieved.

Note that the first particles and the second particles in themicrocapsules may each be formed of a single material selected from aconductive material, an insulating material, a semiconductor material, amagnetic material, a liquid crystal material, a ferroelectric material,an electroluminescent material, an electrochromic material, and amagnetophoretic material, or formed of a composite material thereof.

As the electronic paper, a display device using a twisting ball displaymethod can be used. The twisting ball display method refers to a methodin which spherical particles each colored in white and black arearranged between a first electrode layer and a second electrode layerwhich are electrode layers used for a display element, and a potentialdifference is generated between the first electrode layer and the secondelectrode layer to control orientation of the spherical particles, sothat display is performed.

FIG. 11 illustrates an active matrix electronic paper as one embodimentof a semiconductor device. The electronic paper in FIG. 11 is an exampleof a display device using a twisting ball display method.

Between the first electrode layer 230 connected to the transistor 210and the second electrode layer 231 provided on the second substrate 206,spherical particles 253 each of which includes a black region 255 a, awhite region 255 b, and a cavity 252 around the regions which is filledwith liquid, are provided. A space around the spherical particles 253 isfilled with a filler 254 such as a resin. The second electrode layer 231corresponds to a common electrode (counter electrode). The secondelectrode layer 231 is electrically connected to a common potentialline.

Note that in FIG. 9, FIG. 10, and FIG. 11, a flexible substrate as wellas a glass substrate can be used as the first substrate 201 and thesecond substrate 206. For example, a plastic substrate havinglight-transmitting properties can be used. For plastic, afiberglass-reinforced plastics (FRP) plate, a polyvinyl fluoride (PVF)film, a polyester film, or an acrylic resin film can be used. A sheetwith a structure in which an aluminum foil is sandwiched between PVFfilms or polyester films can also be used.

An insulating layer 221 can be formed using an organic insulatingmaterial or an inorganic insulating material. Note that an organicinsulating material having heat resistance, such as an acrylic resin, apolyimide resin, a benzocyclobutene resin, a polyamide resin, or anepoxy resin is preferably used as a planarizing insulating layer. Otherthan such organic insulating materials, it is possible to use alow-dielectric constant material (a low-k material), a siloxane-basedresin, phosphosilicate glass (PSG), borophosphosilicate glass (BPSG), orthe like. The insulating layer 221 may be formed by stacking a pluralityof insulating layers formed of these materials.

There is no particular limitation on the method for forming theinsulating layer 221, and the insulating layer 221 can be formed,depending on a material thereof, by a sputtering method, a spin coatingmethod, a dipping method, a spray coating method, a droplet dischargingmethod (e.g., an ink-jet method, screen printing, or offset printing),roll coating, curtain coating, knife coating, or the like.

The display device performs display by transmitting light from a lightsource or a display element. Thus, the substrates and the thin filmssuch as insulating layers and conductive layers provided in the pixelportion where light is transmitted have light-transmitting propertieswith respect to light in the visible-light wavelength range.

The first electrode layer 230 and the second electrode layer 231 (eachof which are also referred to as a pixel electrode layer, a commonelectrode layer, a counter electrode layer, or the like) for applying avoltage to the display element may have light-transmitting properties orlight-reflecting properties, which depends on the direction in whichlight is extracted, the position where the electrode layer is provided,and the pattern structure of the electrode layer.

The first electrode layer 230 and the second electrode layer 231 can beformed using a light-transmitting conductive material such as indiumoxide containing tungsten oxide, indium zinc oxide containing tungstenoxide, indium oxide containing titanium oxide, indium tin oxidecontaining titanium oxide, indium tin oxide (hereinafter referred to asITO), indium zinc oxide, or indium tin oxide to which silicon oxide isadded.

The first electrode layer 230 and the second electrode layer 231 can beformed using one kind or plural kinds selected from metal such astungsten (W), molybdenum (Mo), zirconium (Zr), hafnium (Hf), vanadium(V), niobium (Nb), tantalum (Ta), chromium (Cr), cobalt (Co), nickel(Ni), titanium (Ti), platinum (Pt), aluminum (Al), copper (Cu), orsilver (Ag); an alloy thereof; and a nitride thereof.

A conductive composition containing a conductive high molecule (alsoreferred to as a conductive polymer) can be used for the first electrodelayer 230 and the second electrode layer 231. As the conductive highmolecule, a so-called π-electron conjugated conductive polymer can beused. For example, polyaniline or a derivative thereof, polypyrrole or aderivative thereof, polythiophene or a derivative thereof, and acopolymer of two or more of aniline, pyrrole, and thiophene or aderivative thereof can be given.

Since the transistor is easily broken due to static electricity or thelike, a protective circuit for protecting the driver circuit ispreferably provided. The protective circuit is preferably formed using anonlinear element.

As described above, by using any of the transistors, the examples ofwhich are shown in Embodiment 1, a semiconductor device with highreliability can be provided. Note that the transistors, the examples ofwhich are shown in Embodiment 1 can be applied to not only semiconductordevices having the display functions described above but alsosemiconductor devices having a variety of functions, such as a powerdevice which is mounted on a power supply circuit, a semiconductorintegrated circuit such as an LSI, and a semiconductor device having animage sensor function of reading information of an object.

The structures, the methods, and the like described in this embodimentcan be combined as appropriate with any of the structures, the methods,and the like described in the other embodiments.

[Embodiment 3]

A semiconductor device which is one embodiment of the present inventioncan be applied to a variety of electronic devices (including gamemachines). Examples of electronic devices are a television set (alsoreferred to as a television or a television receiver), a monitor of acomputer or the like, a camera such as a digital camera or a digitalvideo camera, a digital photo frame, a mobile phone handset (alsoreferred to as a mobile phone or a mobile phone device), a portable gamemachine, a portable information terminal, an audio reproducing device,and a large-sized game machine such as a pachinko machine. Examples ofelectronic devices each including the semiconductor device described inthe above embodiment are described.

FIG. 12A illustrates a laptop personal computer, which includes a mainbody 301, a housing 302, a display portion 303, a keyboard 304, and thelike. By applying the semiconductor device described in Embodiment 1 or2, the laptop personal computer can have high reliability.

FIG. 12B illustrates a portable information terminal (PDA), whichincludes a display portion 313, an external interface 315, an operationbutton 314, and the like in a main body 311. A stylus 312 is included asan accessory for operation. By applying the semiconductor devicedescribed in Embodiment 1 or 2, the portable information terminal (PDA)with higher reliability can be provided.

FIG. 12C shows an example of an e-book reader. For example, an e-bookreader 320 includes two housings, a housing 321 and a housing 322. Thehousing 321 and the housing 322 are combined with a hinge 325 so thatthe e-book reader 320 can be opened and closed with the hinge 325 as anaxis. With such a structure, the e-book reader 320 can operate like apaper book.

A display portion 323 and a display portion 324 are incorporated in thehousing 321 and the housing 322, respectively. The display portion 323and the display portion 324 may display one image or different images.When the display portion 323 and the display portion 324 displaydifferent images, for example, text can be displayed on a displayportion on the right side (the display portion 323 in FIG. 12C) andimages can be displayed on a display portion on the left side (thedisplay portion 324 in FIG. 12C). By applying the semiconductor devicedescribed in Embodiment 1 or 2, the e-book reader 320 can have highreliability.

FIG. 12C shows an example in which the housing 321 is provided with anoperation portion and the like. For example, the housing 321 is providedwith a power switch 326, operation keys 327, a speaker 328, and thelike. With the operation key 327, pages can be turned. Note that akeyboard, a pointing device, or the like may also be provided on thesurface of the housing, on which the display portion is provided.Furthermore, an external connection terminal (an earphone terminal, aUSB terminal, or the like), a recording medium insertion portion, andthe like may be provided on the back surface or the side surface of thehousing. Moreover, the e-book reader 320 may have a function of anelectronic dictionary.

The e-book reader 320 may send and receive information wirelessly.Through wireless communication, desired book data or the like can bepurchased and downloaded from an e-book server.

FIG. 12D illustrates a mobile phone, which includes two housings, ahousing 330 and a housing 331. The housing 331 includes a display panel332, a speaker 333, a microphone 334, a pointing device 336, a cameralens 337, an external connection terminal 338, and the like. Inaddition, the housing 330 includes a solar cell 340 having a function ofcharge of the portable information terminal, an external memory slot341, and the like. Further, an antenna is incorporated in the housing331. By applying the semiconductor device described in Embodiment 1 or2, the mobile phone can have high reliability.

Further, the display panel 332 is provided with a touch panel. Aplurality of operation keys 335 which are displayed as images isillustrated by dashed lines in FIG. 12D. Note that the mobile phoneincludes a boosting circuit for raising a voltage output from the solarcell 340 to a voltage necessary for each circuit.

In the display panel 332, the display direction can be changed asappropriate depending on a usage pattern. Further, the mobile phone isprovided with the camera lens 337 on the same surface as the displaypanel 332, and thus it can be used as a video phone. The speaker 333 andthe microphone 334 can be used for videophone calls, recording andplaying sound, and the like as well as voice calls. Moreover, thehousings 330 and 331 in a state where they are opened as illustrated inFIG. 12D can be slid so that one overlaps the other; therefore, the sizeof the mobile phone can be reduced, which makes the mobile phonesuitable for being carried.

The external connection terminal 338 can be connected to an AC adapterand various types of cables such as a USB cable, and charging and datacommunication with a personal computer are possible. Moreover, a largeramount of data can be stored by inserting a recording medium to theexternal memory slot 341 and can be moved.

Further, in addition to the above functions, an infrared communicationfunction, a television reception function, or the like may be provided.

FIG. 12E illustrates a digital video camera, which includes a main body351, a display portion (A) 357, an eyepiece 353, an operation switch354, a display portion (B) 355, a battery 356, and the like. By applyingthe semiconductor device described in Embodiment 1 or 2, the digitalvideo camera can have high reliability.

FIG. 12F shows an example of a television set. In a television set 360,a display portion 363 is incorporated in a housing 361. The displayportion 363 can display images. Here, the housing 361 is supported by astand 365. By applying the semiconductor device described in Embodiment1 or 2, the television set 360 can have high reliability.

The television set 360 can be operated by an operation switch of thehousing 361 or a separate remote controller. Further, the remotecontroller may be provided with a display portion for displaying dataoutput from the remote controller.

Note that the television set 360 is provided with a receiver, a modem,and the like. With the use of the receiver, general televisionbroadcasting can be received. Furthermore, when the display device isconnected to a communication network with or without wires via themodem, one-way (from a sender to a receiver) or two-way (between asender and a receiver or between receivers) information communicationcan be performed.

The structures, the methods, and the like described in this embodimentcan be combined as appropriate with any of the structures, the methods,and the like described in the other embodiments.

EXAMPLE 1

In this example, an insulating layer containing a silicon peroxideradical, which is provided in the semiconductor device according to oneembodiment of the present invention, is analyzed by an ESR method, andanalysis results thereof is described.

In this example, a silicon oxide layer or a silicon oxynitride layer wasformed over a 1.1 mm-thick quartz substrate, and divided into samples of20 mm×3 mm. Then, measurement was performed with the two samplesoverlapped.

The conditions of the samples on which the measurement was performed inthis example are shown below.

The conditions for forming Sample 1 were as follows.

-   Film: silicon oxide-   Film formation method: RF sputtering method-   Target: silicon target-   Film formation gas: Ar (10 sccm), O₂ (40 sccm)-   Electric power: 3 kW (13.56 MHz)-   Pressure: 0.6 Pa-   T-S distance: 60 mm-   Substrate temperature in film formation: room temperature-   Thickness: 300 nm

The conditions for forming Sample 2 were as follows.

-   Film: silicon oxide-   Film formation method: RF sputtering method-   Target: silicon target-   Film formation gas: Ar (10 sccm), O₂ (40 sccm)-   Electric power: 3 kW (13.56 MHz)-   Pressure: 0.6 Pa-   T-S distance: 60 mm-   Substrate temperature in film formation: 100° C.-   Thickness: 300 nm

The conditions for forming Sample 3 were as follows.

-   Film: silicon oxide-   Film formation method: RF sputtering method-   Target: silicon target-   Film formation gas: Ar (40 sccm), O₂ (10 sccm)-   Electric power: 3 kW (13.56 MHz)-   Pressure: 0.6 Pa-   T-S distance: 60 mm-   Substrate temperature in film formation: 100° C.-   Thickness: 300 nm

The conditions for forming Sample 4 were as follows.

-   Film: silicon oxide-   Film formation method: RF sputtering method-   Target: quartz target-   Film formation gas: Ar (40 sccm), O₂ (10 sccm)-   Electric power: 1.5 kW (13.56 MHz)-   Pressure: 0.4 Pa-   T-S distance: 60 mm-   Substrate temperature in film formation: 100° C.-   Thickness: 300 nm

The conditions for forming Sample 5 were as follows.

-   Film: silicon oxynitride-   Film formation method: plasma CVD method-   Source gas: SiH₄ (25 sccm), N₂O (1000 sccm)-   Electric power: 35 W (13.56 MHz)-   Pressure: 133.3 Pa-   Electrode-substrate distance: 20 mm-   Substrate temperature in film formation: 200° C.-   Thickness: 300 nm

Sample 6 was a quartz substrate for reference.

Not that for analysis by an ESR method, E500 CW-EPR spectrometermanufactured by Bruker BioSpin K.K. was used.

FIG. 13 shows ESR analysis result of Sample 1. FIG. 14 shows ESRanalysis result of Sample 2. FIG. 15 shows ESR analysis result of Sample3. FIG. 16 shows ESR analysis result of Sample 4. FIG. 17 shows ESRanalysis result of Sample 5. FIG. 18 shows ESR analysis result of Sample6. Note that the measurement for ESR analysis was performed underconditions where the microwave electric power was 0.1 mW, ModulationAmplitude was 0.5 G, Conversion Time was 400 msec, the number of timesscanned was 25, and the measurement temperature was room temperature.

Here, signals at g value=2.0003 and 2.0019 represent a silicon suboxideradical ((O—)₃Si.), and signals at g value=2.0016 and 2.0078 represent asilicon peroxide radical.

In Samples 1 to 4, silicon suboxide radicals were detected. In addition,in Samples 1, 2, and 4, silicon peroxide radicals were detected. InSamples 5 and 6, neither a silicon suboxide nor a silicon peroxideradical was detected. It was found that silicon peroxide radical wasdetected in the case even where the proportion of oxygen (O₂/(O₂+Ar))was 20% and a quartz target was used, although a silicon peroxideradical was not detected in the case where the proportion of oxygen(O₂/(O₂+Ar)) was 20% and a silicon target was used. Further, in Sample 5which was manufactured by a plasma CVD method, neither a siliconsuboxide radical nor a silicon peroxide radical was detected. Note thatTable 1 shows whether a silicon suboxide radical or a silicon peroxideradical was detected in Samples 1 to 6.

TABLE 1 Sample silicon suboxide radical silicon peroxide radical Sample1 detected detected Sample 2 detected detected Sample 3 detected notdetected Sample 4 detected detected Sample 5 not detected not detectedSample 6 not detected not detected

Thus, it is preferable to employ a sputtering method and use a quartztarget to form an insulating layer having a silicon peroxide radical. Inthe case where a silicon target is used, it is preferable to increasethe rate of O₂/(O₂+Ar).

EXAMPLE 2

In this example, a transistor formed using one embodiment of the presentinvention is described.

FIG. 19 illustrates a structure of the transistor of this example.

The transistor in FIG. 19 includes a base insulating layer 502 providedover a substrate 500, an oxide semiconductor layer 506, a sourceelectrode 508 a and a drain electrode 508 b, a gate insulating layer 512provided over the source electrode 508 a and the drain electrode 508 b,a gate electrode 514 provided over the gate insulating layer 512, aprotective insulating layer 516 provided over the gate electrode 514,and a source wiring 518 a and a drain wiring 518 b connected to thesource electrode 508 a and the drain electrode 508 b, respectively,through openings provided in the protective insulating layer 516.

In this example, a 0.7-mm-thick glass substrate was used as thesubstrate 500, a 300-nm-thick silicon oxide layer was formed as the baseinsulating layer 502, a 30-nm-thick In—Ga—Zn—O-based non-single-crystallayer was formed as the oxide semiconductor layer 506, a 100-nm-thicktungsten layers were formed as the source electrode 508 a and the drainelectrode 508 b, a 20-nm-thick silicon oxynitride layer was formed asthe gate insulating layer 512, a stack of a 30-nm-thick tantalum nitridelayer and a 370-nm-thick tungsten layer was formed as the gate electrode514, a 300-nm-thick silicon oxide layer was formed as the protectiveinsulating layer 516, and stacks of a 50-nm-thick titanium layer, a100-nm-thick aluminum layer, and a 5-nm-thick titanium layer were formedas the source wiring 518 a and the drain wiring 518 b.

In the transistor of this example, a base insulating layer containing asilicon peroxide radical is used as the base insulating layer 502,whereby fluctuation in the threshold voltage and fluctuation in thethreshold voltage after a BT test are reduced. In this example, asilicon oxide layer is used as the base insulating layer containing asilicon peroxide radical.

Other formation conditions of the silicon oxide layer were as follows.

-   Film formation method: RF sputtering method-   Target: quartz target-   Film formation gas: Ar (25 sccm), O₂ (25 sccm)-   Electric power: 1.5 kW (13.56 MHz)-   Pressure: 0.4 Pa-   T-S distance: 60 mm-   Substrate temperature: 100° C.

The formation conditions of the oxide semiconductor layer 506 in thetransistor of this example were as follows.

-   Film formation method: DC sputtering method-   Target: In—Ga—Zn—O (In₂O₃:Ga₂O₃:ZnO=1:1:2 [molar ratio]) target-   Film formation gas: Ar (30 sccm), O₂ (15 sccm)-   Electric power: 0.5 kW (DC)-   Pressure: 0.4 Pa-   T-S distance: 60 mm-   Substrate temperature: 200° C.

After the oxide semiconductor layer 506 was formed, heat treatment wasperformed at 350° C. under a nitrogen atmosphere for an hour using aresistance heating furnace.

FIG. 20 shows drain current (Ids)-gate voltage (Vgs) measurement resultsin the transistor of this example. Note that the measurement wasperformed at 25 points on a substrate surface. The measurement resultsof the 25 points are all shown in FIG. 20. The channel length L is 2 μm,and the channel width W is 50 μm. Note that the voltage Vds between thesource electrode and the drain electrode of the transistor was set to 3V.

According to FIG. 20, it was found that there was no variation in thesubstrate surface of the transistor of this example. Note that theaverage threshold voltage of the points was 0.27 V.

Next, the BT test in this example is described. The transistor on whichthe BT test is performed has a channel length L of 3 μm and a channelwidth W of 50 μm. In this example, first, the substrate temperature wasset to 25° C. and the voltage Vds between the source electrode and thedrain electrode was set to 3 V to perform the Ids-Vgs measurement of thetransistor.

Next, the substrate stage temperature was set to 150° C., and the sourceelectrode and the drain electrode of the transistor were set to 0 V and0.1 V, respectively. Then, a negative voltage was applied to the gateelectrode so that electric-field intensity applied to the gateinsulating layer was 2 MV/cm, and the condition was kept for an hour.Next, the voltage of the gate electrode was set to 0 V. After that, thesubstrate temperature was set to 25° C. and the voltage Vds between thesource electrode and the drain electrode was set to 3 V to perform theIds-Vgs measurement of the transistor. FIG. 21A shows the Ids-Vgsmeasurement results before and after the BT test.

In FIG. 21A, a thin line 522 shows the Ids-Vgs measurement resultsbefore the BT test, and a thick line 524 shows the Ids-Vgs measurementresults after the BT test. It is found that the threshold voltagefluctuates in a negative direction by 0.07 V after the BT test, ascompared to the measurement results before the BT test.

In a similar manner, another transistor for measurement was prepared,and the substrate temperature was set to 25° C. and the voltage Vdsbetween the source electrode and the drain electrode was set to 3 V toperform the Ids-Vgs measurement of the transistor. The channel length Lof the transistor is 3 μm, and the channel width W thereof is 50 μm.

Next, the substrate stage temperature was set to 150° C., and the sourceelectrode and the drain electrode of the transistor were set to 0 V and0.1 V, respectively. Then, a negative voltage was applied to the gateelectrode so that electric-field intensity applied to the gateinsulating layer was 2 MV/cm, and the condition was kept for an hour.Next, the voltage of the gate electrode was set to 0 V. After that, thesubstrate temperature was set to 25° C. and the voltage Vds between thesource electrode and the drain electrode was set to 3 V to perform theIds-Vgs measurement of the transistor. FIG. 21B shows the Ids-Vgsmeasurement results before and after the BT test.

In FIG. 21B, a thin line 532 shows the Ids-Vgs measurement resultsbefore the BT test, and a thick line 534 shows the Ids-Vgs measurementresults after the BT test. It is found that the threshold voltagefluctuates in a positive direction by 0.19 V after the BT test, ascompared to the measurement results before the BT test.

As described above, it is found that the transistor of this example hassmall variation in the threshold voltage of the substrate surface andsmall fluctuation in the threshold voltage between before and after a BTtest.

This application is based on Japanese Patent Application Serial No.2010-117753 filed with the Japan Patent Office on May 21, 2010, theentire contents of which are hereby incorporated by reference.

The invention claimed is:
 1. A semiconductor device comprising: asubstrate; a gate electrode; an oxide semiconductor layer comprisingindium and zinc; a source electrode and a drain electrode electricallyconnected to the oxide semiconductor layer; a first insulating layerbetween the gate electrode and the oxide semiconductor layer; and asecond insulating layer comprising a silicon peroxide radical, whereinthe oxide semiconductor layer is provided between the first insulatinglayer and the second insulating layer, wherein the second insulatinglayer is in contact with the oxide semiconductor layer, and wherein theoxide semiconductor layer is dehydrated or dehydrogenated.
 2. Thesemiconductor device according to claim 1, wherein the gate electrodeoverlaps with the oxide semiconductor layer with the first insulatinglayer interposed therebetween, and wherein the oxide semiconductor layeris provided between the gate electrode and the substrate.
 3. Thesemiconductor device according to claim 1, wherein the source electrodeand the drain electrode are provided between the first insulating layerand the oxide semiconductor layer.
 4. The semiconductor device accordingto claim 1, wherein the source electrode and the drain electrode areprovided between the second insulating layer and the oxide semiconductorlayer.
 5. The semiconductor device according to claim 1, wherein theoxide semiconductor layer overlaps with the gate electrode with thefirst insulating layer interposed therebetween, and wherein the gateelectrode is provided between the substrate and the oxide semiconductorlayer.
 6. The semiconductor device according to claim 1, wherein thefirst insulating layer comprises a silicon peroxide radical.
 7. Thesemiconductor device according to claim 1, wherein the oxidesemiconductor layer comprises a channel region, a source region and adrain region, and wherein the source region and the drain region havelower resistance than the channel region.
 8. The semiconductor deviceaccording to claim 1, wherein the silicon peroxide radical comprises thestructure represented by Si—O—O●.
 9. The semiconductor device accordingto claim 1, wherein the first insulating layer comprising the siliconperoxide radical has signals at g value=2.0016and 2.0078 in a spectrumobtained by an electron spin resonance method.
 10. The semiconductordevice according to claim 1, wherein a hydrogen concentration of theoxide semiconductor layer is lower than 1×10¹⁸ cm⁻³.
 11. Thesemiconductor device according to claim 1, wherein a carrierconcentration of the oxide semiconductor layer is lower than 1×10¹⁴cm⁻³.
 12. A semiconductor device comprising an insulating layer incontact with an oxide semiconductor layer, wherein the oxidesemiconductor layer comprises indium and zinc, wherein the insulatinglayer comprises a silicon peroxide radical, and wherein the oxidesemiconductor layer is dehydrated or dehydrogenated.
 13. Thesemiconductor device according to claim 12, wherein the silicon peroxideradical comprises the structure represented by Si—O—O●.
 14. Thesemiconductor device according to claim 12, wherein the insulating layerhas signals at g value=2.0078 and 2.0016 in a spectrum obtained by anelectron spin resonance method.
 15. The semiconductor device accordingto claim 12, wherein a hydrogen concentration of the oxide semiconductorlayer is lower than 1×10¹⁸ cm⁻³.
 16. The semiconductor device accordingto claim 12, wherein a carrier concentration of the oxide semiconductorlayer is lower than 1×10¹⁴ cm⁻³.